Preparation of halogenated ethers



Patented Dec. 17, 1935 PATENT OFFICE PREPARATION OF HALOGENATED n'rnsasNorman D. Scott, Niagara Falls, N. Y., assignor to E. I. du Pont deNemours & Company, Inc., Wilmington, DeL, a corporation of Delaware NoDrawing. Application August 4, 1932, 1 Serial No. 627,539

19 Claims. (01. 260-151) CHz=CH2+ClCH2OCHa- ClCH2 CHz-CHzOCHa.

Similarly, from propylene and chlormethyl ether I have obtainedgamma-chlorbutyl methyl ether;

In this case it will be noted that the chlorine atom adds on to themiddle carbon atom of the propylene, in the secondary position, asmight, perhaps, be predicted by analogy with the known manner ofaddition of hydrohalogens to propylene.

The addition of the methoxy methylene group to the other side of theolefine linkage results as shown above, in the formation of a normalbutane derivative. .This was shown experimentally by treating thechlorbutyl methyl ether with strong NaOH to split out HCl, resulting inthe formation of CH:CH=CI-ICH2OCH3 which was then converted by catalytichydrogenation with a platlnum oxide catalyst, into normal butyl methylether.

1 have carried out analogous reactions using amylene as the olefinehydrocarbon. This reacts even more vigorously than propylene which inturn reacts more vigorously than ethylene. In addition to condensationsinvolving monochlormethyl ether, I have carried out the similarcondensation reactions using the following alphahalogenated ethers:symmetric. dichlordimethyl ether, monobrommethyl etherfalpha chlorethylether, and monochlormethyl isopropyl ether.

The best conditions and methods for carrying outthe reactions will ofcourse vary with the particular olefine hydrocarbon and alphahalogenated ether. In general the use of a catalyst has been foundadvisable though not necessary in some cases. I have found thatmoderately easily hydrolizable metal halides, soluble in the halogenatedether-olefine reaction mixture, such as,

BiCla, BiBr3, SbCl5, sncli, ZnClz, FeClz, A1013, form satisfactorycatalysts. The optimum combination of temperature, pressure, catalystconcentration, and duration of reaction will obviously vary withparticular combination of mate- 5 rials employed. The following examplesare given by way of further illustration of methods of carrying outthese reactions:

Example 1 external cooling, and controlled rate of admitting thepropylene, the temperature was kept from exceeding 70 C. and averagedabout C. during the period of saturation which was one and one- 20 halfhours. The final pressure in the bomb was 150 lbs. The bomb was cooledin ice water, the excess propylene vented, and the liquid poured out.This crude product measured 1490 cc. and weighed 1676 gms: After washingwith water, 5 drying and distilling, a fraction was collected at 121-131C. weighing 938 gms. which was very largely chlorbutyl methyl ether. Atotal of 358 cc. of higher boiling material was largely achlorheptylmethyl ether, boiling point about 205 C. 30 The molecular weight andcomposition of this substance indicate that it is derived from thereaction of two molecules of propylene with one molecule of chlormethylether. It most probable. formula appears to be 35 Example 2 A solutionof 10 gms. ZnCl: in 200 cc. chlormethyl ether was treated with 10 cc.portions of amylene until a total of 250 cc. had been added during aperiod of about 1 hour. The flask was shaken after each addition and thetemperature 'room temperature, abmrption oi gas.

'- ether.

was kept below 30 C. by occasionally immersing in ice water. 7 I mirturewas thoroughly washed with water at When the reaction had ceased the 50C. 250 cc. oi oily material was obtained.

7 The material was distilled, yielding 200cc. of an oil which boiled,with some decomposition, at about 150 (J. Rapid redistillation underreduced pressure at 80" 0. gave a relatively pure product which wasidentified as monochlorhexyl methyl e l Example 3 I 200 cc. of chlormethyl ether and 150 cc. of amylenewere mixed together and allowed tostand over night at room temperature. After. washing with hot water 50cc. of anoil'remained.

500 cc. oi chlormetlurl ether, containing 25 gins.

- oi BlCls in solution'was placed'in a steel bomb mounted on a shaker,and connected to a cylinder 01' compressed ethylene. The reactionmixture was heated to 80 C. and treated with ethylene at 100-8 00.1bs.pressure for 7 hours. The excess gas was vented after cooling the bomb,and the liquid products poured out. On fractionation 191 grams 01' amaterial boiling at 109-115 C. was

obtained; this wasverylargely' gamma chlor propyl methyl ether.

Y Example Asolution of 5 gms. ZnCl: in 100 cc. of somewhat impuredichlordimethyl ether was shaken with propylene at atmospheric pressure,at about until there was no further The crude product containingdichlor-dibutyl ether was then washed with water and diluted NaOH untilsubstantially neutral. After drying with CaCh this was distilled undervacu 23 s cc. were collected boiling mainly at 130-135 0., at 10 mm. Hg.pressure': Determination of chlorine'fin this material showed, it tocontain 32.5%, as

The term alpha halogenated ether as used in the specification and claimsrefers to halogens on a carbon atom next'to the ether oxygen atom. Iclaim' 1. Method to. the production oi. halogenated aliphatic higherethers which comprises reacting an alpha halogenated aliphatic etherwith an organic'compound containing an olefinic linkage betweentwocarbon atoms.

3. Method for the production oi chlorinated,

aliphatic higher ethers which comprises reacting an alpha chlorinatedaliphatic I ether with an sanic co p d containing an cleiinlc l nkagebetween two carbon atoms. v

'drocarbon.

with 35.6% in pure dichlordibutyl 4. Method for the production ofchlorinated aliphatic higher ethers which comprises reacting an alphachlorinated aliphatic ether with an oleflne hydrocarbon.

' '5.Process which comprises reactinganalpha I halogenatedv aliphaticether with an organic compound having an oleflne. hydrocarbon group. 1

6. Process which comprises reacting an alpha halogenated ether with anoleiine hydrocarbon.

7. Process which comprises reacting an alpha l0 chlorinated ether withan oleflne hydrocarbon. 8. Process which comprises reactingmonochlormethylimethyl ether with an organic compound containing anoleflnic linkage betweentwo carbon atoms. l5 9. Process which comprisesreacting symmetric dichlordimethyl ether with an organic compoundcontaining an oleiinic linkage between two carbon atoms.

10. Process which comprises reacting monochlormethyl methyl ether withan oleflne hydrocarbon.

11. Process which comprises reacting symmetric dichlordimethyl etherwith an oleflne 'hy- 26 12. Method for the production of halogenatedaliphatic higher ethers which comprises reacting an alpha halogenatedaliphatic ether with an organic compound containing an oleflnic' linkagebetween two carbon atoms in the presence oi a $0 moderately easilyhydrolizable metal halide soluble in the reaction mixtur v 13. Methodfor the production of halogenated aliphatic higher ethers whichcomprises reacting an alpha halogenated aliphatic ether with an oleilnehydrocarbon in the presence 01' a moderately easily hydrolizahle metalhalide soluble in the reaction'mixture. f

14. Method for the production 01 halogenated aliphatic higher etherswhich comprises reacting 40 an alpha halogenated aliphatic ether with anorganic compound containing an oleflnic link-' a e between two carbonatoms in the presence of a bismuth halide.

15. Method for the production 01' halogenated aliphatic higher etherswhich comprises reacting an alpha halogenated aliphatic ether with anoleiine hydrocarbon in the presence of a bismuth halide.

16. Method for the production oi halogenated aliphatic higher etherswhich comprises reacting an alpha halogenated aliphatic ether with anolefine hydrocarbon in the presence 01' bismuth chloride.

17. Method for the production of halogenated aliphatic higher etherswhich comprises reacting an alpha halogenated aliphatic ether with anoleflne hydrocarbon in the presence of zinc chloride. I

18. Method for the production or halogenated aliphatic higher etherswhich comprises reacting an alpha halogenated'aliphatic other with anoleflne hydrocarbon in the presence of tin chloride. do 19. As a newproduct, gamma chlor primary. I

bu lme lether.

w my NORMAN D. sco'rr.

